Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/22—Emulsion polymerisation
  • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents

Definitions

• the present invention relates to the emulsion polymerization of olefinic monomers and/or of conjugated diolefins, and more particularly to the emulsion polymerization of vinyl chloride to form homopolymers and copolymers thereof.
• the well known emulsion polymerization of olefinic monomers employs a variety of surfactants, but these surfactants often give rise to unstable latices and/or result in low conversion.
• the surfactant remains in the film and, particularly in the case of sulfur-containing surfactants, causes undesired color changes when the film is subjected to heat or light.
• the present invention provides a process for the emulsion polymerization of an olefinic monomer using a phosphate ester of a straight chain alkanol having 8 to 10 carbon atoms.
• the monomer to be polymerized may be at least one olefinic compound containing one or more carbon-to-carbon double bonds.
• Monomers which may be polymerized are the vinyl halides, i.e., vinyl chloride, vinyl fluoride, vinyl bromide and vinyl iodide; the vinylidene halides, i.e., vinylidene chloride, vinylidene fluoride, vinylidene bromide, and vinylidene iodide; 2-halogenobutadienes; esters of unsaturated alcohols with mono- and polybasic saturated and unsaturated acids, such as vinyl acetate, allyl acetate, diallyl maleate, etc.; esters of saturated alcohols with mono- and polybasic unsaturated acids, such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, haloacrylates, diethyl maleate, diethyl fumarate, etc.
• Homopolymers or copolymers of dienes may also be prepared by the method of the invention, and suitable diene monomers include butadiene, 2,3-dimethyl-1,3-butadiene, isoprene, piperylene, 3-furyl-1,3-butadiene, 3-methoxy-1,3-butadiene, etc.
• the surfactant to be used in the improved process has the general formula: ##EQU1## or where R is straight chain alkyl of 8 to 10 carbon atoms, and M is hydrogen or a metal, ammonium or amino cation. Suitable metal cations are sodium, potassium and lithium. Suitable amino cations are derived from ammonia and primary, secondary and tertiary aliphatic, aromatic and/or heterocyclic amines. The preferred ammonium and amino cations have the formula: ##EQU2## wherein R 1 , R 2 and R 3 are independently hydrogen, alkyl of 1 to 6 carbon atoms, hydroxyalkyl of 1 to 6 carbon atoms and cycloalkyl of 3 to 6 carbon atoms.
• the phosphate ester used as the surfactant in the method of the present invention may be prepared by esterifying P 2 O 5 with an alkanol of the formula ROH, where R is as defined above, to obtain the phosphate ester of formula I or II above, where M is hydrogen.
• the resulting product can then be neutralized with a base MOH, where M is a metal, or with ammonium hydroxide or an amine, to provide the desired ester of formula I or II, where M is a metal, ammonium or amino cation.
• the emulsion polymerization is carried out under conventional conditions of temperature, pressure, agitation and the like, using watersoluble initiators known in the art for this purpose, such as ammonium persulfate, potassium persulfate, hydrogen peroxide, and various redox systems, such as chlorate-bisulfite systems. While batch operation is predominantly used in the United States for emulsion polymerization, continuous operation may be used, if desired.
• a suitable recipe is as follows:
• additives such as plasticizers, may be charged to the autoclave along with this reaction mixture.
• a phosphate ester surfactant suitable for use in the present invention was prepared as follows. 426 g. of P 2 O 5 (anhydrous) was added under nitrogen to a mixture of 1020 g. of "Alfol 810" and 3 ml of a 50% aqueous solution of hypophosphorous acid, with cooling to keep the temperature below 50°C, over a period of 1 3/4 hours. The reaction mass was then heated to 100°C for 1 hour and then cooled to 50°-60°C. Three milliliters of a 36% aqueous solution of hydrogen peroxide was added to the cooled reaction product to obtain a water white colored mixture of the mono- and diphosphoric acid ester in a yield of 1045 g. The product analyzed 23% of the monoester
• This phosphate ester is neutralized with sodium hydroxide to form the sodium salt thereof, and designated surfactant A.
• the water, surfactant and potassium chloride are mixed and the pH adjusted to 8.7 by addition of a few drops of 50% NaOH.
• the sodium bicarbonate is then added and the solution charged to a previously nitrogen purged and evacuated 1/2-gallon glass reactor.
• the solution in the reactor is purged and evacuated five more times.
• the monomers are added from previously nitrogen purged and evacuated cylinders and finally the potassium persulfate previously dissolved in 40ml distilled water (included in 386 g total purged with nitrogen in an addition cylinder) is added and the contents heated to 50°C while stirring at 200 RPM.
• the starting pressure on reaching 50° is near 90-95 psig. Reaction rate was judged by pressure drop.
• the following Example compares the thermal stability of films made from the latex obtained from the method of the present invention to films made using sulfur-containing surfactants.
• the water, surfactant, and potassium chloride are mixed and pH adjusted to 8.7 by addition of 50% NaOH.
• the sodium bicarbonate is then added and the solution charged to a previously nitrogen purged and evacuated 1/2-gallon glass reactor.
• the dibutyl phthalate is then charged and the mixture is purged and evacuated five more times.
• Monomers are added from previously nitrogen purged and evacuated cylinders, and finally the potassium persulfate previously dissolved in 40 ml distilled water is added and the contents heated to 50°, while stirring at 200 RPM.
• the starting pressure at 50°C is 80-90 psig.
• the water, surfactant and potassium chloride are mixed and the pH adjusted to 7.0 by addition of sodium hydroxide.
• This solution is then charged to the autoclave along with the ethyl acrylate and potassium persulfate.
• the autoclave is then purged with nitrogen and evacuated prior to addition of the vinyl chloride from a previously purged cylinder.
• the contents of the autoclave are then heated to 55°C. and held until the pressure drop indicates all monomers have been consumed.
• Surfactant A gave a fluid latex with no coagulum.
• the phosphate ester of 2-ethylhexanol, namely ##EQU4## gave massive coagulum and the polymerization failed to go to completion. This illustrates the need for straight chain C 8 to C 10 alkyl in the phosphate ester.

Priority Applications (6)

Applications Claiming Priority (1)

Publications (1)

Family

ID=23964054

Family Applications (1)

Country Status (6)

Cited By (9)

Families Citing this family (3)

Citations (2)

Family Cites Families (2)

• 1974
  • 1974-08-02 US US05/494,333 patent/US3963688A/en not_active Expired - Lifetime
• 1975
  • 1975-06-30 CA CA230,523A patent/CA1044391A/en not_active Expired
  • 1975-07-04 GB GB28348/75A patent/GB1506639A/en not_active Expired
  • 1975-07-18 JP JP50088786A patent/JPS5134979A/ja active Pending
  • 1975-07-24 DE DE19752533043 patent/DE2533043A1/de active Pending
  • 1975-07-24 FR FR7523100A patent/FR2280652A1/fr active Granted

Patent Citations (2)

Also Published As

Similar Documents

Legal Events